Thermoplastic composition for laser direct structuring

Abstract

This invention relates to a thermoplastic composition comprising: a) 20 to 90 wt% of a thermoplastic resin, b) a laser-direct structuring additive, c) optionally, ceramic filler particles without laser-direct structuring additive function, and d) 0.1 to 5.0 wt% of an acid-modified polymer, wherein b) comprises b1) a conductive metal oxide, wherein the conductive oxide has a maximum of 5 x 10⁻⁶ ppm. 3 The resistivity is Ω·cm, and it contains at least a metal of Group n and Group (n+1) of the periodic table, where n is an integer from 3 to 13, and / or b2) calcium copper titanate.

Description

[0001] This invention relates to thermoplastic compositions suitable for use in laser direct structuring methods. The invention also relates to molded parts comprising said compositions. Furthermore, the invention relates to a method for producing circuit carriers by providing conductive tracks to said molded parts via laser irradiation and subsequent metallization, and the circuit carriers thereby obtained.

[0002] With the latest developments in mobile phones, including smartphones, numerous studies have been conducted on methods for manufacturing antennas within mobile phones. A particular need exists to enable three-dimensional design of antennas within mobile phones. Laser direct structuring (hereinafter occasionally referred to as "LDS") is one known method for forming such three-dimensional antennas. LDS is a technique for forming a coating layer, typically by irradiating the surface of a resin molded article containing LDS additives with a laser, thereby activating only the laser-irradiated portion, and then applying metal to the activated portion. The desirable characteristic of this technique is the ability to directly fabricate metal structures, such as antennas, on the surface of a resin base without the use of adhesives or the like.

[0003] The development of smartphones has led to a demand for materials with high dielectric constants (DC) used in antenna fabrication. High DC allows for a reduction in antenna size. Current existing technologies do not offer LDS materials with high DC. In particular, polycarbonate-based compositions have relatively low DC.

[0004] US2009 / 0292051 discloses a thermoplastic composition comprising 10 to 90 wt% of a thermoplastic base resin, 0.1 to 30 wt% of a laser direct structuring additive (LDS), and 10 to 80 wt% of a ceramic filler. According to US2009 / 0292051, the LDS additive contributes to increasing the dielectric constant, thus requiring less ceramic filler to achieve the same level of dielectric constant in the composition. The LDS additive is a mixture of heavy metal oxides, spinel, or copper salts. The ceramic filler used in the examples is a mixture of BaTiO3 and TiO2 in a 39 / 21 ratio. In the examples, the thermoplastic base resin is poly(aryl ether), PA66, PPA, or PPO.

[0005] One of the most important properties of LDS compositions is plating capability. EP2998361B1 describes a conductive oxide comprising at least two metals and also having a 5x10... 3 A novel LDS additive with a resistivity of Ω·cm or less, wherein the laser direct structuring additive contains at least a metal from Group n and a metal from Group (n+1) of the periodic table, where n is an integer from 3 to 13. This conductive oxide was found to have high plating susceptibility.

[0006] Another important requirement is the prevention of polymer degradation. WO2009 / 024496 has shown that LDS additives degrade aromatic polycarbonates (as demonstrated by a decrease in Mw), which in turn leads to a significant increase in MFI and a severe reduction in impact strength. WO2009 / 024496 addresses this problem by using a rubbery polymer to prevent degradation.

[0007] Therefore, LDS compositions with high DC are desirable, in which polymer degradation is prevented.

[0008] WO2020 / 126188 discloses a thermoplastic composition comprising: a) a thermoplastic resin, b) a laser direct structuring additive, and c) ceramic filler particles without the function of the laser direct structuring additive, wherein at least 80% by weight of c) is TiO2, wherein the composition has a loss tangent of at most 0.014 when measured at 40 GHz.

[0009] One object of the present invention is to provide an LDS composition wherein the above and / or other requirements are met.

[0010] Therefore, the present invention provides a thermoplastic composition comprising the following:

[0011] a) 20 to 90% by weight of thermoplastic resin,

[0012] b) Laser-directed structuring additives.

[0013] c) Optionally, ceramic filler particles that do not have laser-directly structured additive functionality, and

[0014] d) 0.1 to 5.0% by weight of acid-modified polymer,

[0015] Where b) includes

[0016] b1) A conductive metal oxide, wherein the conductive oxide has a density of at most 5 x 10⁻⁶ 3 The resistivity is Ω·cm, and it contains at least metals from Group n and Group (n+1) of the periodic table, where n is an integer from 3 to 13, and / or

[0017] b2) Calcium copper titanate.

[0018] The inventors have observed that the LDS additive used in this invention not only achieves good plating properties but also significantly contributes to increasing the density (DC) of the composition. However, the inventors have also observed that the LDS additive used in this invention leads to the degradation of the thermoplastic resin. The inventors have surprisingly discovered that adding an acid-modified polymer to this composition prevents this degradation. Therefore, according to the present invention, high DC is achieved while preventing polymer degradation.

[0019] a) Thermoplastic resin

[0020] Thermoplastic resins may include resins such as polycarbonates (especially aromatic polycarbonates), polyamides, polyesters, polyesteramides, polystyrene, polymethyl methacrylate, polyphenylene ether, liquid crystal polymers (LCPs), polyether ether ketones (PEEKs), cyclic olefin (co)polymers (COPs), or combinations thereof. Resins may be homopolymers, copolymers, or mixtures thereof, and may be branched or unbranched.

[0021] Examples of suitable polyamides (PAs) are aliphatic polyamides such as PA6, PA46, PA66, PA6 / 66, PA11, and PA12, which can be branched polyamides; semi-aromatic polyamides such as MXD6, PA6I / 6T, PA66 / 6T, and PA4T; fully aromatic polyamides; and copolymers and blends of the listed polyamides. Examples of suitable polyesters are polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). Preferred polyesters are polyethylene terephthalate and polybutylene terephthalate. Polyphenylene ethers are often used in combination with polyamides or polystyrene. Examples of suitable LCPs include... E845i LDS, E840i LDS, TECACOMP LCP LDS black4107 are commercialized. Suitable PEEK instances are commercialized as TECACOMP PEEKLDS. Suitable COP instances are commercialized as ZEONEX RS420-LDS Cyclo Olefin Polymer.

[0022] Thermoplastic resins may also contain rubber-like polymers. Examples of rubber-like polymers are described in WO-A-2009024496, which is incorporated herein by reference. Rubber-like polymers are or contain elastomeric (i.e., rubber-like) polymers having a Tg preferably less than about 10°C, more particularly less than about -10°C, or even more particularly from about -20°C to -80°C.

[0023] In some embodiments, the compositions according to the invention comprise less than 2.5% by weight of a rubbery polymer. An advantage of the invention is that polymer degradation is prevented even for compositions containing small amounts or no rubbery polymer.

[0024] In a preferred embodiment, the thermoplastic resin is a polycarbonate-based resin. The polycarbonate-based resin may be polycarbonate or a blend of polycarbonate and a rubbery polymer such as acrylonitrile butadiene styrene rubber (ABS). The polycarbonate may be a homopolymer, copolymer, or mixture thereof, and may be branched or unbranched. Suitable polycarbonate-based resins are described, for example, in US2009 / 0292048, which is incorporated herein by reference.

[0025] Polycarbonates comprising aromatic carbonate chain units include components (compositions) having structural units of formula (I):

[0026] -R 1 -O-CO-O-(I)

[0027] Where R 1 The group is an aromatic, aliphatic, or alicyclic group. Advantageously, R 1 It is an aromatic organic group, and in an alternative embodiment, it is a group of formula (II):

[0028] -A 1 -Y 1 -A 2 -(II)

[0029] Where A 1 and A 2 Each of them is a monocyclic divalent aryl group, and Y 1 Is A 1 With A 2 Separate bridging groups having 0, 1, or 2 atoms. In one exemplary embodiment, one atom will connect A... 1 With A 2 Separate. Illustrative examples of such groups are -O-, -S-, -S(O)-, -S(O2)-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,1]-bicycloheptide, ethoxy, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecanidene, cyclododecaneidene, adamantaneidene, etc. In another embodiment, zero atoms will A 1 With A 2 Separately, an illustrative example is bisphenol. The bridging group Y... 1 It can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylene, or isopropylene.

[0030] Suitable aromatic polycarbonate resins include polycarbonates made from at least a divalent phenol and a carbonate precursor, for example, by commonly known interfacial polymerization or melt polymerization methods. Suitable divalent phenols are compounds having one or more aromatic rings containing two hydroxyl groups, each hydroxyl group being directly attached to a carbon atom forming part of the aromatic ring. Examples of such compounds include:

[0031] 4,4'-Dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 4,4-bis(4-hydroxyphenyl)heptane, bis-(3,5-dimethyl-4-hydroxyphenyl) 1,1-Bis-(4-hydroxyphenyl)-cyclohexane, 1,1-Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane, 2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4,4'-dihydroxyphenyl)methane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, bis-4-hydroxyphenyl sulfone, bis-4-hydroxyphenyl sulfone.

[0032] Carbonate precursors can be carbonyl halogenides, halogenated carboxylates, or carbonates. Examples of carbonyl halogens are carbonyl chlorides and carbonyl bromides. Suitable examples of halogenated carboxylates are bis-halogenated carboxylates of divalent phenols such as hydroquinone or glycols such as ethylene glycol. Suitable examples of carbonates are diphenyl carbonate, di(chlorophenyl) carbonate, di(bromophenyl) carbonate, di(alkylphenyl) carbonate, phenyltolyl carbonate, and mixtures thereof. Although other carbonate precursors may be used, carbonyl halogens, and especially carbonyl chlorides (also known as phosgene), are preferred.

[0033] The aromatic polycarbonate resin in the composition according to the invention can be prepared using a catalyst, an acid acceptor, and a compound for controlling the molecular weight.

[0034] Examples of catalysts are tertiary amines such as triethylamine, tripropylamine, and N,N-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, and quaternary phosphonium compounds such as methyltriphenylphosphonium bromide.

[0035] Examples of organic acid acceptors include pyridine, triethylamine, and dimethylaniline. Examples of inorganic acid acceptors include hydroxides, carbonates, bicarbonates, and phosphates of alkali metals or alkaline earth metals.

[0036] Examples of compounds used to control molecular weight are monovalent phenols such as phenol, p-alkylphenols, p-bromophenols, and secondary amines.

[0037] rubber-like polymer

[0038] Examples of rubbery polymers that can be blended with resins such as polycarbonate are described in WO-A-2009024496, which is incorporated herein by reference. A rubbery polymer is or contains an elastomer (i.e., a rubber-like) polymer having a Tg preferably less than about 10°C, more particularly less than about -10°C, or even more particularly from about -20°C to -80°C.

[0039] Preferably, the amount of rubbery polymer in thermoplastic resin a) is 0 to 60% by weight of the amount of thermoplastic resin a), for example, 1 to 50% by weight, 5 to 40% by weight, or 10 to 30% by weight.

[0040] Examples of elastomeric polymers include polyisoprene; butadiene-based rubbers such as polybutadiene, styrene-butadiene random copolymers and block copolymers, hydrogenated versions of said block copolymers, acrylonitrile-butadiene copolymers and butadiene-isoprene copolymers; acrylate-based rubbers such as ethylene-methacrylate and ethylene-butyl acrylate, acrylate-butadiene copolymers, for example acrylic elastomers such as butyl acrylate-butadiene copolymers; siloxane-based rubbers such as polyorganosiloxanes, such as polydimethylsiloxane, polymethylphenylsiloxane and dimethyl-diphenylsiloxane copolymers; and other elastomeric polymers such as ethylene-propylene random copolymers and block copolymers, copolymers of ethylene and [α]-olefins, copolymers of ethylene and aliphatic vinyl groups such as ethylene-vinyl acetate, and ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-hexadiene copolymers, butene-isoprene copolymers, and chlorinated polyethylene, and these substances may be used alone or in combination of two or more.

[0041] Particularly preferred elastomeric polymers include ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer), and MBS (methyl methacrylate-butadiene-styrene copolymer). Particularly preferred graft copolymers are acrylonitrile-butadiene-styrene rubber (ABS), methyl methacrylate-butadiene-styrene rubber (MBS), or mixtures of these copolymers, because of the high compatibility between the polycarbonate matrix and such copolymers, allowing these copolymers to be uniformly dispersed within the polycarbonate matrix. This reduces arbitrary degradation of the thermoplastic resin that may be caused by certain types of components b). From an economic point of view, acrylonitrile-butadiene-styrene (ABS) is even more preferred. Any commercially available ABS can be used. Particularly preferred acrylonitrile-butadiene-styrene (ABS) is acrylonitrile-butadiene-styrene with a rubber content of 10 to 50 parts by weight, preferably 10 to 40 parts by weight, and even more preferably 10 to 30 parts by weight.

[0042] In a particularly preferred embodiment, thermoplastic resin a) is a blend of 45 to 75% by weight polycarbonate, 5 to 40% by weight ABS and 0 to 10% by weight MBS, wherein the amounts are relative to the thermoplastic resin a).

[0043] In some embodiments, the rubber is a graft copolymer comprising an elastomeric component containing Si. This has advantages in improving the flame retardancy of the composition. The graft copolymer is formed by graft copolymerizing the Si-containing elastomeric component with a monomer component to which it can be copolymerized. The elastomeric component generally has a glass transition temperature of at most 0°C, preferably at most -20°C, more preferably -30°C.

[0044] As a graft copolymer, a core / shell graft copolymer is preferred, wherein the core is a Si-containing elastomer component. The Si-containing elastomer component is preferably a polyorganosiloxane.

[0045] The graft copolymer is preferably a graft copolymer containing a polyorganosiloxane, which is preferably prepared by polymerization of 5 to 60 parts by weight of a vinyl monomer (l) in the presence of 40 to 95 parts by weight of polyorganosiloxane particles (ll) (the sum of (l) and (ll) is 100 parts by weight), as described, for example, in US2005 / 0143520. Examples of vinyl monomers (l) include, for example, aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene and p-butylstyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; (meth)acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate and hydroxyethyl methacrylate; and carboxyl-containing vinyl monomers such as itaconic acid, (meth)acrylic acid, fumaric acid and maleic acid. If desired, the vinyl monomer (l) may comprise a polyfunctional monomer having at least two polymerizable unsaturated bonds per molecule. Examples of polyfunctional monomers include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and divinylbenzene. The vinyl monomer (l) may be used alone or in combination. The polyorganosiloxane particles (ll) are preferably prepared by emulsion polymerization of the constituent components. Normal seed emulsion polymerization can be applied to graft copolymerization and can be achieved by free radical polymerization of the vinyl monomer (l) in the latex of the polyorganosiloxane particles (ll).

[0046] These graft copolymers containing polyorganosiloxanes are commercially available, such as Kane Ace MR01 and Kane Ace MR02 from Kaneka Company.

[0047] Other suitable graft copolymers that include Si-containing elastomeric components include Metalatn S-2001, Metalatn S-2200 and Metalatn SX-005 from Mitsubishi Rayon.

[0048] In a particularly preferred embodiment, the thermoplastic resin a) is a blend of 80 to 99 wt% polycarbonate and 1 to 20 wt% graft copolymer comprising an elastomeric component containing Si, wherein the amounts are relative to the thermoplastic resin a).

[0049] In some embodiments, the thermoplastic resin a) is or comprises a polysiloxane-polycarbonate copolymer. Examples of polysiloxane-polycarbonate copolymers are described, for example, in US5380795 and WO09040772. This also has advantages in terms of improved flame retardancy of the composition.

[0050] Therefore, in some preferred embodiments, component a) is

[0051] - A blend consisting of 45 to 75% by weight of polycarbonate and 5 to 40% by weight of ABS, wherein the amounts are relative to the thermoplastic resin a).

[0052] - A blend consisting of 45 to 75% by weight polycarbonate, 5 to 40% by weight ABS, and 1 to 10% by weight MBS, wherein the amounts are relative to the thermoplastic resin a).

[0053] - A blend comprising 80 to 99 wt% polycarbonate and 1 to 20 wt% graft copolymer comprising an elastomeric component containing Si, wherein the graft copolymer is a core / shell graft copolymer, wherein the core is a polyorganosiloxane, and wherein the amount is relative to the thermoplastic resin a).

[0054] The amount of a) in the composition of the present invention is 20 to 90% by weight relative to the total weight of the composition, for example at least 30% by weight, at least 40% by weight, at least 50% by weight or at least 60% by weight and / or at most 85% by weight, at most 80% by weight, at most 75% by weight, at most 70% by weight, at most 67% by weight or at most 65% by weight.

[0055] Thermoplastic resins a) particularly polycarbonate-based resins or polycarbonates may have melt flow rates of, for example, 5 to 25 dg / min or 8 to 20 dg / min at 300°C according to ISO 1133-1:2011. In some cases, thermoplastic resins a) comprise different polycarbonates with different melt flow rates, such as virgin polycarbonate and post-consumption recycled (PCR) polycarbonate, or are composed of them. The MFR of PCR polycarbonate is largely limited by the articles in which it is used, such as beverage bottles (e.g., water bottles), CDs, and automotive lighting. For example, PCR polycarbonate obtained from beverage bottles tends to have a relatively low MFR, for example, 5 to 10 dg / min at 300°C according to ISO 1133-1:2011.

[0056] b) Laser-directed structuring additives

[0057] LDS additives contain b1) conductive metal oxides as described below and / or b2) calcium copper titanate.

[0058] A particularly preferred embodiment of the present invention relates to a thermoplastic composition comprising the following:

[0059] a) 20 to 90% by weight of thermoplastic resin,

[0060] b) Laser-directed structuring additives.

[0061] c) Optionally, ceramic filler particles that do not have laser-directly structured additive functionality, and

[0062] d) 0.1 to 5.0% by weight of acid-modified polymer,

[0063] Where b) includes

[0064] b1) Conductive metal oxides containing zinc and aluminum, preferably aluminum-doped zinc oxide, and / or

[0065] b2) Calcium copper titanate.

[0066] b1) Conductive metal oxides

[0067] The conductive metal oxide in the LDS additive has 5x10 3 Ω·cm or smaller, preferably 8x10 2 Ω·cm or less, more preferably 7x10 2 Ω·cm or less, or even more preferably 5x10 2 Resistivity of Ω·cm or less. There is no specific lower limit, but it can be, for example, 1 x 10⁻⁶. 1 Ω·cm or larger, more particularly 1x10 2 Ω·cm or greater.

[0068] As used herein, the resistivity of the conductive oxide typically refers to the powder resistivity. The resistivity of the conductive metal oxide can be measured, for example, via a multimeter on a molded body of the conductive metal oxide formed by pressurizing a fine powder of the conductive metal oxide. More specifically, the resistivity of the conductive metal oxide can be measured via a multimeter on 10g of a fine powder of the conductive metal oxide at 100kg / cm². 2 Measurements were taken on a molded body of a conductive metal oxide produced under pressure. The pressure was applied to 10g of fine powder of conductive metal oxide loaded into a cylinder with an inner diameter of 25mm, wherein the cylinder may be internally coated with polytetrafluoroethylene (PTFE). The fine powder was pressurized to give the molded body a packing density of 20%. More specifically, resistivity was measured using a tester from Yokogawa Electric Corporation, model 3223, by loading 10g of fine powder of conductive oxide into a cylinder with an inner diameter of 25mm and internally coated with polytetrafluoroethylene (PTFE). In the cylinder and at 100kg / cm 2 Apply pressure to it (bulk density 20%).

[0069] The conductive metal oxide contains at least a metal of group n and a metal of group (n+1) of the periodic table, where n is an integer from 3 to 13. The conductive metal oxide contains at least a metal of group 3 and group 4, a metal of group 4 and group 5, a metal of group 5 and group 6, a metal of group 6 and group 7, a metal of group 7 and group 8, a metal of group 8 and group 9, a metal of group 9 and group 10, a metal of group 10 and group 11, a metal of group 11 and group 12, a metal of group 12 and group 13, or a metal of group 13 and group 14.

[0070] Suitable metals for Group n or Group n+1 of the periodic table include, for example, Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), and Group 13 (aluminum, gallium, indium, etc.).

[0071] Suitable metals for Group n of the periodic table also include metals from Group 3 (scandium and yttrium).

[0072] Suitable metals for group n+1 of the periodic table also include metals from group 14 (germanium, tin, etc.).

[0073] Preferably, n is an integer from 10 to 13, more preferably 12 or 13, and most preferably 12.

[0074] Preferably, the conductive metal oxide comprises metals of Group 12 and Group 13.

[0075] Preferably, the amount of the group n metal relative to the total amount of group n and group n+1 metals in the conductive metal oxide is 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less; or, relative to the total amount of group n and group n+1 metals in the conductive metal oxide, the amount of the group n+1 metal is 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less. The lower limit is not particularly limited, but should be 0.0001 mol% or greater. Particularly preferably, the conductive metal oxide is an oxide of a group n metal doped with a group n+1 metal. High plating applicability is achieved.

[0076] Furthermore, the metals of Group n and Group (n+1) of the periodic table described above preferably constitute 98% by weight or more of the metal components contained in the conductive metal oxide.

[0077] Particularly preferably, the conductive metal oxide comprises zinc and aluminum. Most preferably, the conductive metal oxide is aluminum-doped zinc oxide.

[0078] In some preferred embodiments, b) comprises or contains particles of b1). The amount of particles in b1) relative to the amount of b) may be, for example, 10 to 100% by weight, preferably at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99.0% by weight, at least 99.5% by weight, at least 99.9% by weight, or 100% by weight.

[0079] b2) Calcium copper titanate

[0080] LDS additives may include b2) calcium copper titanate.

[0081] In some preferred embodiments, b) comprises or contains particles of b2). The amount of particles in b2) relative to the amount of b) may be, for example, 10 to 100% by weight, preferably at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99.0% by weight, at least 99.5% by weight, at least 99.9% by weight, or 100% by weight.

[0082] b) Other components

[0083] In some preferred embodiments, b) comprises or consists of particles consisting of a core and a shell covering the core, wherein the shell is made of b1) and / or b2). The core is preferably made of a material having a high dielectric constant. The weight ratio between the core and the shell can be any value, for example, from 1:2 to 100:1, as long as b1) and / or b2) are used as LDS additives. The amount of particles consisting of the core and the shell covering the core (wherein the shell is made of b1) and / or b2) relative to the amount of b) can be, for example, from 10 to 100% by weight, for example, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99.0% by weight, at least 99.5% by weight, at least 99.9% by weight, or 100% by weight.

[0084] In some preferred embodiments, b) consists of particles of b1) and / or b2), or particles consisting of a core and a shell covering the core, wherein the shell is made of b1) and / or b2). b) may also consist of particles of b1) and / or b2) and particles consisting of a core and a shell covering the core, wherein the shell is made of b1) and / or b2).

[0085] Therefore, in these preferred embodiments, the composition does not contain materials with laser direct structuring additive functionality other than b1) and / or b2). For example, the composition may contain less than 0.1 wt% or less than 0.05 wt% of a mixture of heavy metal oxide spinel, such as copper chromium oxide spinel; copper salts, such as basic copper phosphate, copper phosphate, copper sulfate, cuprous thiocyanate; or a combination including at least one of the aforementioned LDS additives. For example, relative to the total composition, the composition may contain less than 0.1 wt% or less than 0.05 wt% of the following LDS additives: which are not particles of b1) and / or b2) or particles consisting of a core and a shell covering the core, wherein the shell is made of b1) and / or b2).

[0086] The terms “laser direct structuring additive” and “material with laser direct structuring additive function” are understood to mean materials capable of forming a coating on an article prepared by: 1) molding a sample made by adding 10 parts by weight of a candidate material of LDS additive to 100 parts by weight of a thermoplastic resin such as polycarbonate; 2) irradiating the sample with a laser; and 3) subjecting the irradiated sample to electroless plating. For example, step 2) could be irradiating the sample with a YAG laser at a wavelength of 1064 nm at an output of 13 W, a frequency of 20 kHz, and a scan rate of 2 m / s. For example, step 3) could be subjecting the irradiated sample to electroless plating using a MID Copper 100XB Strike plating bath (from MacDermidPerformance Solutions).

[0087] When b) consists of particles consisting of a core and a shell covering the core (wherein the shell is made of b1) and / or b2), the core is preferably selected such that it contributes to achieving the desired radio frequency performance of the composition according to the invention.

[0088] Preferably, the core is made of ceramic material, preferably selected from ceramic materials of metal oxides, metal silicates, metal borides, metal carbides and metal nitrides.

[0089] Suitable examples of metal oxides include magnesium oxide, titanium oxide (e.g., TiO2), zinc oxide, copper oxide, cerium oxide, niobium oxide, tantalum oxide, yttrium oxide, zirconium oxide, aluminum oxide (e.g., bauxite and / or pyrolytic bauxite), CaTiO3, MgZrSrTiO6, MgTiO3, MgAl2O4, BaZrO3, BaSnO3, BaNb2O6, BaTa2O6, WO3, MnO2, SrZrO3, SnTiO4, ZnO3, and ZnO3. rTiO4, CaZrO3, CaSnO3, CaWO4, MgTa2O6, MgZrO3, La2O3, CaZrO3, MgSnO3, MgNb2O6, SrNb2O6, MgTa2O6, Ta2O3, Barium titanate (BaTiO3), Strontium titanate (SrTiO3), Barium Strontium titanate, Strontium-doped Lanthanum manganate, Lanthanum aluminum oxide (LaAlO3), Copper cadmium titanate (CdCu3Ti4O12), Ca 1-x La x MnO3, (Li,Ti)-doped NiO, lanthanum strontium copper oxide (LSCO), yttrium barium copper oxide (YBa2Cu3O7), lead zirconate titanate, and lanthanum-modified lead zirconate titanate.

[0090] Examples of silicates are Na₂SiO₃, LiAlSiO₄, Li₄SiO₄, BaTiSi₃O₉, Al₂Si₂O₇, ZrSiO₄, KAlSi₃O₈, NaAlSi₃O₈, CaAl₂Si₂O₈, CaMgSi₂O₆, and Zn₂SiO₄. Note that mica and talc are not preferred as cores because they do not contribute to achieving the desired RF performance.

[0091] Examples of borides are lanthanum boronide (LaB6), cerium boronide (CeB6), strontium boronide (SrB6), aluminum boronide, calcium boronide (CaB6), titanium boronide (TiB2), zirconium boronide (ZrB2), vanadium boronide (VB2), tantalum boronide (TaB2), chromium boronide (CrB and CrB2), molybdenum boronide (MoB2, Mo2B5 and MoB), and tungsten boronide (W2B5).

[0092] Examples of carbides are silicon carbide, tungsten carbide, tantalum carbide, iron carbide, and titanium carbide.

[0093] Examples of nitrides include silicon nitride, boron nitride, titanium nitride, aluminum nitride, and molybdenum nitride.

[0094] Preferably, the core is made of a ceramic material selected from metal oxides, metal borides, metal carbides and metal nitrides.

[0095] Preferably, the core is made of a metal oxide, more preferably titanium dioxide and / or barium titanate, and most preferably titanium dioxide.

[0096] Preferably, the amount of b1), b2), or the sum of b1) and b2) is at least 0.1% by weight and at most 80% by weight relative to the total composition. Preferably, the amount of b1), b2), or the sum of b1) and b2) is at least 1.0% by weight, at least 3.0% by weight, at least 5.0% by weight, at least 10% by weight, at least 15% by weight, at least 16% by weight, at least 17% by weight, at least 18% by weight, at least 19% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 31% by weight, at least 32% by weight, at least 33% by weight, at least 34% by weight, or at least 35% by weight relative to the total composition. Preferably, the amount of b1), b2), or the sum of b1) and b2) is at most 75% by weight, at most 70% by weight, at most 65% by weight, or at most 60% by weight relative to the total composition. Higher amounts of b1), b2), or the sum of b1) and b2) result in better radio frequency performance.

[0097] Preferably, the amount of b) is at least 0.1% by weight and at most 80% by weight relative to the total composition. Preferably, the amount of b) relative to the total composition is at least 1.0% by weight, at least 3.0% by weight, at least 5.0% by weight, at least 10% by weight, at least 15% by weight, at least 16% by weight, at least 17% by weight, at least 18% by weight, at least 19% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 31% by weight, at least 32% by weight, at least 33% by weight, at least 34% by weight, or at least 35% by weight. Preferably, the amount of b) relative to the total composition is at most 75% by weight, at most 70% by weight, at most 65% by weight, or at most 60% by weight.

[0098] Preferably, as determined by light scattering technology, the LDS additive has a particle size d90 of up to 8 μm, more preferably up to 5 μm, more preferably up to 4 μm, and more preferably up to 2 μm.

[0099] Preferably, as determined by light scattering technology, the LDS additive has a particle size d50 of up to 5 μm, more preferably up to 4 μm, and even more preferably up to 2 μm.

[0100] It has been found that LDS additives with smaller dimensions impart good mechanical strength to the compositions according to the invention.

[0101] Particle size can be determined, for example, using a Malvern Mastersize particle size analyzer via light scattering techniques. This can be done according to, for example, ISO 13320-1:2009.

[0102] In some embodiments, b) may further include a material having laser direct structuring additive functionality, preferably a metal compound selected from:

[0103] Copper-containing spinels, such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel;

[0104] Copper salts, such as copper hydroxide, copper phosphate, copper sulfate, and cuprous thiocyanate;

[0105] Organometallic complexes, such as palladium / palladium-containing heavy metal complexes;

[0106] Tin oxides, such as antimony tin oxide (antimony-doped tin oxide), bismuth tin oxide (bismuth-doped tin oxide), aluminum tin oxide (aluminum-doped tin oxide), and molybdenum tin oxide (molybdenum-doped tin oxide);

[0107] Zn x Ni 1-X Fe2O4, where x is greater than 0.60 and less than 0.85, and

[0108] Its combination.

[0109] When present, the amount of the other material having laser direct structuring additive function is typically 0.1 to 10% by weight, for example 1.0 to 5.0% by weight, relative to the total composition.

[0110] In some embodiments, the compositions according to the invention are substantially free of materials other than b1) or b2) that have laser direct structuring additive functions. For example, the compositions may contain less than 0.1% by weight, less than 0.05% by weight, or less than 0.01% by weight of a metal compound selected from the group consisting of:

[0111] Copper-containing spinels, such as copper-chromium oxide spinel, copper-molybdenum oxide spinel, and copper-chromium-manganese oxide spinel; copper salts, such as copper hydroxide, copper phosphate, copper sulfate, and cuprous thiocyanate; organometallic complexes, such as palladium / palladium-containing heavy metal complexes; tin oxides, such as antimony-tin oxide (antimony-doped tin oxide), bismuth-tin oxide (bismuth-doped tin oxide), aluminum-tin oxide (aluminum-doped tin oxide), and molybdenum-tin oxide (molybdenum-doped tin oxide); Zn x Ni 1-X Fe2O4, wherein x is greater than 0.60 and less than 0.85; and combinations thereof.

[0112] c) Ceramic filler particles that do not have laser-direct structuring additive function

[0113] The composition according to the invention may further include component c), which is particles of ceramic material without LDS additive function.

[0114] Preferably, the amount of c) relative to the total composition is up to 75% by weight, for example up to 60%, 50%, or 40% by weight. Preferably, the amount of c) is up to 30% by weight relative to the total composition. When the amount of c) is up to 30% by weight, the desired flame retardancy can be obtained.

[0115] The amount of c) may also be up to 20% by weight, less than 10% by weight, or up to 9% by weight relative to the total composition. The amount of c) may also be 0% by weight relative to the total composition. Advantageously, the desired properties can be obtained without using a significant amount of ceramic filler particles.

[0116] However, it is also advantageous if the composition according to the invention contains a certain amount of c), because c) is more cost-effective than b) for obtaining the desired dielectric properties. Furthermore, c) can more effectively improve the mechanical properties of the composition, such as impact strength, than b). Preferably, the amount of c) is at least 0.1 wt%, at least 1.0 wt%, or at least 3.0 wt% relative to the total composition. In some embodiments, the amount of c) is at least 0.1 wt% and less than 10 wt% relative to the total composition. In some embodiments, the amount of c) is at least 10 wt% and at most 27 wt% relative to the total composition.

[0117] In this specification, the term "particles of material" is understood to mean a particulate component of material, regardless of its shape (spherical, whisker-like, fibrous, etc.). This term is used to distinguish it from the core of the core-shell particles described with respect to component b).

[0118] Preferably, the ceramic material is selected from metal oxides, metal silicates, metal borides, metal carbides, and metal nitrides.

[0119] Preferably, the ceramic material is selected from metal oxides, metal borides, metal carbides, and metal nitrides.

[0120] Preferably, the ceramic material is a metal oxide, and more preferably selected from one or more of titanium dioxide, barium titanate, and barium strontium titanate.

[0121] In some preferred embodiments, at least 80% by weight of the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is titanium dioxide. This results in a low loss tangent at high frequencies. Preferably, the amount of titanium dioxide relative to the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight.

[0122] In some preferred embodiments, at least 80% by weight of the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is barium titanate. Preferably, the amount of barium titanate relative to the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight.

[0123] In some preferred embodiments, at least 80% by weight of the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is barium strontium titanate. This results in an extremely high flame retardancy in the composition. Preferably, the amount of barium strontium titanate relative to the ceramic filler particles without laser direct structuring additive function present in the composition according to the invention is at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight.

[0124] Preferably, the total amount of b1), b2), and c) is at least 35% by weight, more preferably at least 40% by weight, relative to the total composition. This results in a high dielectric constant. Preferably, the total amount of b1), b2), and c) is at most 70% by weight or at most 65% by weight, relative to the total composition.

[0125] Preferably, the total amount of b) and c) is at least 35% by weight, more preferably at least 40% by weight, relative to the total composition. Preferably, the total amount of b) and c) is at most 70% by weight or at most 65% by weight, relative to the total composition.

[0126] Preferably, the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.0, preferably at least 1.2, at least 1.5, at least 1.8, at least 2.0, at least 2.5, at least 3.0, at least 3.5 or at least 4.0.

[0127] Preferably, the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.0, preferably at least 1.2, at least 1.5, at least 1.8, at least 2.0, at least 2.5, at least 3.0, at least 3.5 or at least 4.0.

[0128] The sum of a), b) and c)

[0129] Preferably, the total amount of components a), b) and c) is 90 to 99.9% by weight of the total composition, for example, 95 to 99% by weight.

[0130] d) Acid-modified polymers

[0131] Acid-modified polymers can be polymers obtained by modifying polymers with compounds having functional groups, such as unsaturated carboxylic acids.

[0132] Preferably, the acid-modified polymer is an acid-modified olefin polymer or an acid-modified styrene polymer, more preferably an acid-modified olefin polymer.

[0133] The olefin polymer is preferably polyethylene or polypropylene.

[0134] The olefin polymer preferably has a weight-average molecular weight of 1,000 to 5,000.

[0135] Preferably, the acid-modified polymer is a polymer modified by an unsaturated carboxylic acid, wherein the unsaturated carboxylic acid is preferably selected from acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride and maleic monoamide.

[0136] Most preferably, the acid-modified olefin polymer is maleic anhydride-modified polyethylene.

[0137] Suitable examples include commercially available Mitsui Hi-WAX1105A manufactured by Mitsui Chemicals, Inc., with an Mv of 1500, a density of 940 kg / m³, and an acid value of 60 mg / g of KOH.

[0138] The amount of d) relative to the total composition is 0.1 to 5.0% by weight, preferably 0.3 to 3.0% by weight, more preferably 0.5 to 1.5% by weight.

[0139] The sum of a), b), c) and d)

[0140] Preferably, the total amount of components a), b), c), and d) is 90 to 100% by weight of the total composition, for example, 90 to 99.9%, 92 to 99.0%, or 95 to 98% by weight relative to the total composition. Preferably, the total amount of components a), b), c), and d) is at least 96%, at least 97%, at least 98%, or at least 99% by weight relative to the total composition.

[0141] e) Flame retardants

[0142] Preferably, the thermoplastic composition according to the invention further comprises e) a flame retardant.

[0143] Preferably, the amount of component e) relative to the total composition is 0 to 15% by weight, for example at least 0.01% by weight, at least 0.05% by weight, or at least 0.1% by weight and / or at most 10% by weight, at most 5% by weight, or at most 1.0% by weight.

[0144] Flame retardants can be inorganic or organic.

[0145] Examples of inorganic flame retardants include sulfonates such as potassium perfluorobutane sulfonate (Rimar salt) and potassium diphenyl sulfone sulfonate; and salts formed by reacting, for example, alkali metal or alkaline earth metal salts (preferably lithium, sodium, potassium, magnesium, calcium, and barium salts) with inorganic acid complex salts, such as oxoanions, alkali metal and alkaline earth metal salts of carbonate, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, BaCO₃, and BaCO₃, or fluoride anion complexes, such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄, K₂SiF₆, and / or Na₃AlF₆. Inorganic flame retardants are advantageous for maintaining the Vicat temperature.

[0146] Examples of organic flame retardants include organophosphates and / or organic compounds containing phosphorus-nitrogen bonds.

[0147] One type of exemplary organophosphate is an aromatic phosphate of the formula (GO)3P=O, wherein each G is independently alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl, provided that at least one G is an aromatic group. Two G groups may be linked together to provide a cyclic group, such as diphenyl pentaerythritol diphosphate, which is described by Axelrod in U.S. Patent No. 4,154,775. Other suitable aromatic phosphates can be, for example, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl)p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, etc. Specific aromatic phosphates are those in which each G is aromatic, such as triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, etc.

[0148] Difunctional or polyfunctional aromatic phosphorus compounds are also useful, such as the following compound.

[0149]

[0150] Each G 1 Independently, it is a hydrocarbon group having 1 to 30 carbon atoms; each G 2Independently, it is a hydrocarbon group or hydroxyl group having 1 to 30 carbon atoms; each X is independently bromine or chlorine; m is 0 to 4, and n is 1 to 30. Examples of suitable difunctional or polyfunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), hydroquinone bis(diphenyl) phosphate, and bisphenol-A bis(diphenyl) phosphate (each, their oligomeric and polymeric counterparts, etc.). Methods for preparing the above-mentioned difunctional or polyfunctional aromatic compounds are described in British Patent No. 2,043,083.

[0151] Other examples of organic flame retardants include phosphazene compounds, particularly those represented as follows.

[0152]

[0153] Where t is an integer from 3 to 25, R 5 and R 6 They can be the same or different, and each represents an aryl or alkylaryl group, and

[0154]

[0155] Where u is an integer from 3 to 10,000, R 9 It indicates at least one group selected from -N=P(OR)3 group, -N=P(OR)3 group, etc. 8 )3 group, —N=P(O)OR 7 Group and —N=P(O)OR 8 The species of the group, and R 10 Indicates at least one selected from —P(OR) 7 )4 group, —P(OR) 8 )4 group, —P(O)(OR 7 )2 group and —P(O)(OR 8 Species of the )2 group, R 7 and R 8 They can be the same or different, and each represents an aryl or alkylaryl group.

[0156] Examples of such phosphazene compounds represented by the above two formulas include cyclic and / or chain C1-6 alkyl C6-20 aryloxyphosphazenes such as phenoxyphosphazenes, (poly)tolyloxyphosphazenes (e.g., o-tolyloxyphosphazenes, m-tolyloxyphosphazenes, p-tolyloxyphosphazenes, o, m-tolyloxyphosphazenes, o, p-tolyloxyphosphazenes, m, p-tolyloxyphosphazenes and o, m, p-tolyloxyphosphazenes) and (poly)xyloxyphosphazenes; and cyclic and / or chain C6-20 aryl C1-10 alkyl C6-20 aryloxyphosphazenes such as (poly)phenoxytolyloxyphosphazenes (e.g., phenoxy-o-tolyloxyphosphazenes, phenoxy-m-tolyloxyphosphazenes) Phosphazenes, phenoxy-p-tolyloxyphosphazenes, phenoxy-o,m-tolyloxyphosphazenes, phenoxy-o,p-tolyloxyphosphazenes, phenoxy-m,p-tolyloxyphosphazenes and phenoxy-o,m,p-tolyloxyphosphazenes), (poly)phenoxydimethyloxyphosphazenes and (poly)phenoxytolyloxydimethyloxyphosphazenes, wherein preferred examples include cyclic and / or chain phenoxyphosphazenes, cyclic and / or chain C1-3 alkyl C6-20 aryloxyphosphazenes, C6-20 aryloxy C1-3 alkyl C6-20 aryloxyphosphazenes (e.g. cyclic and / or chain tolyloxyphosphazenes and cyclic and / or chain phenoxytolylphenoxyphosphazenes).

[0157] Examples of such phosphazene compounds include cyclic phenoxyphosphazene (trade name SPB-100) from Otsuka Chemical Co., Ltd. and cyclic phenoxyphosphazene (trade name Rabitle FP-110) from Fushimi Pharmaceutical Co., Ltd.

[0158] This phosphazene compound is described in detail in US2012 / 0301766,

[0133] -

[0142] , which is incorporated herein by reference.

[0159] The thermoplastic compositions of the present invention may be substantially free of chlorine and bromine, particularly chlorine and bromine flame retardants, which can be defined as having a bromine and / or chlorine content of less than 100 ppm, less than 75 ppm, or less than 50 ppm relative to the total composition.

[0160] Preferably, the molded part of the composition has at least a UL94V2 rating (i.e., V2, V1 or V0 rating) at a thickness of 3.0 mm (±10%).

[0161] Preferably, the molded part of the composition has at least a UL94V2 rating (i.e., V2, V1 or V0 rating) at a thickness of 1.5 mm (±10%).

[0162] It was observed that, unlike other types of LDS additives, the LDS additive used in this invention allows the desired UL94 rating to be achieved. It was further surprisingly found that adding the acid-modified polymer according to the invention has no substantially detrimental effect on flame retardancy. Therefore, with this invention, the desired UL94 rating can be achieved by adding a flame retardant in an appropriate amount.

[0163] The sum of a), b), c), d), and e)

[0164] Preferably, the total amount of components a), b), c), d), and e) is 90 to 100% by weight of the total composition, for example, 90 to 99.9%, 92 to 99.0%, or 95 to 98% by weight relative to the total composition. Preferably, the total amount of components a), b), c), d), and e) is at least 96%, at least 97%, at least 98%, or at least 99% by weight relative to the total composition.

[0165] Component f) Anti-drip agent

[0166] The thermoplastic composition according to the invention may further include f) an anti-drip agent.

[0167] Preferably, the amount of component f) is 0-2.0 wt% or 0.05-2.0 wt% relative to the total composition, more preferably 0.1-1.5 wt%, more preferably 0.2-1.0 wt%. The presence of component f) is optional, and therefore the composition according to the invention may contain very little component f) or no component f) at all. For example, the amount of component f) relative to the total composition may be less than 0.05 wt%, less than 0.01 wt%, or 0 wt%.

[0168] Suitable examples of anti-drip agents include fluoropolymers such as polytetrafluoroethylene (PTFE). Fluoropolymers can be fluoropolymers that form fibrils, such as PTFE, or fluoropolymers that form non-fibrils, such as PTFE.

[0169] Anti-drip agents can be in the form of an aqueous dispersion of a fluoropolymer. In this case, the dispersion contains a sufficient amount, for example, at least 30% by weight or at least 50% by weight of the fluoropolymer.

[0170] Anti-drip agents can be in the form of a mixture of a fluoropolymer and another polymer (e.g., an encapsulated fluoropolymer). In this case, the dispersion contains a sufficient amount, for example, at least 30% by weight or at least 50% by weight of the fluoropolymer in the mixture. The other polymer can be, for example, an acrylate copolymer or styrene-acrylonitrile. Examples of mixtures of fluoropolymers and acrylate polymers are commercially available as METABLEN A-3800 from Mitsubishi Rayon. The encapsulated fluoropolymer can be prepared by polymerizing the polymer in the presence of the fluoropolymer.

[0171] Preferably, the anti-drip agent is a mixture of a fluoropolymer and another polymer, such as an encapsulated fluoropolymer. This type of anti-drip agent is easier to handle than anti-drip agents in dispersion form because feeding into the extruder is easier and water does not need to be removed from the composition.

[0172] The sum of a), b), c), d), e), and f)

[0173] Preferably, the total amount of components a), b), c), d), e), and f) is 90 to 100% by weight of the total composition, for example, 90 to 99.9%, 92 to 99.0%, or 95 to 98% by weight relative to the total composition. Preferably, the total amount of components a), b), c), d), e), and f) is at least 96%, at least 97%, at least 98%, or at least 99% by weight relative to the total composition.

[0174] Other additives (g)

[0175] The thermoplastic composition according to the invention may further comprise one or more other additives (g) from 0 to 10% by weight relative to the total weight of the composition. These include conventional additives such as stabilizers against heat or thermal oxidative degradation, stabilizers against hydrolytic degradation, stabilizers against light (especially UV light) degradation and / or photo-oxidative degradation, and processing aids such as mold release agents and lubricants. Suitable examples of such additives and their conventional amounts are stated above in Kunststoff Handbuch, 3 / 1. The total amount of said additives is typically 0 to 5% by weight, for example 0.1 to 3% by weight or 0.3 to 1% by weight.

[0176] The sum of a), b), c), d), e), f), and g)

[0177] Preferably, the total amount of components a), b), c), d), e), f), and g) is 100% by weight of the total composition.

[0178] Glass filler h)

[0179] The compositions according to the invention may or may not further contain h) glass fillers such as glass fibers. It will be understood that h) glass fillers are different from c) ceramic filler particles that do not have laser direct structuring additive functionality.

[0180] In some embodiments, the composition according to the invention comprises less than 5% by weight, preferably less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or 0% by weight relative to the total weight of the composition.

[0181] Preferably, the total amount of components a), b), c), d), e), f), g), and h) is 100% by weight of the total composition.

[0182] It will be understood that g) additives are different from e) flame retardants, f) anti-drip agents and h) glass fillers, that is, g) additives do not include e) flame retardants, f) anti-drip agents and h) glass fillers.

[0183] Components b) and d) as described above, and optional components, can be introduced into thermoplastic resin a) using suitable mixing equipment such as a single-screw or twin-screw extruder, preferably a twin-screw extruder. Preferably, thermoplastic resin granules are introduced into the extruder along with at least components b) and d) and extruded, then quenched in a water bath, and then granulated. Therefore, the invention also relates to a method for preparing thermoplastic compositions according to the invention by melt mixing of components a) and b) and d) as described above, and optional components.

[0184] nature

[0185] Preferably, the composition has a dielectric constant of at least 3.5 or at least 4.0 measured at 1 GHz and / or at least 3.5 or at least 4.0 measured at 6 GHz. This DC can be achieved by selecting appropriate amounts of b1) and / or b2) and optional component c).

[0186] Preferably, the dielectric constant of the composition according to the invention, measured at 1 GHz, is at least 3.5, more preferably at least 4.0, more preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, and more preferably at least 5.0.

[0187] Preferably, the loss tangent (Df) of the composition according to the invention, measured at 1 GHz, is at most 0.014, more preferably at most 0.010, and even more preferably at most 0.007. A low Df minimizes energy loss (heat) and / or maximizes the energy of radiation.

[0188] Preferably, the dielectric constant of the composition according to the invention, measured at 6 GHz, is at least 3.5, more preferably at least 4.0, more preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, and more preferably at least 5.0.

[0189] Preferably, the loss tangent of the composition according to the invention, measured at 6 GHz, is at most 0.014, more preferably at most 0.010, and even more preferably at most 0.007.

[0190] Preferably, the dielectric constant of the composition according to the invention, measured at 40 GHz, is at least 3.5, more preferably at least 4.0, more preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, and more preferably at least 5.0.

[0191] Preferably, the loss tangent of the composition according to the invention, measured at 40 GHz, is at most 0.014, more preferably at most 0.010, and more preferably at most 0.007.

[0192] In this paper, the dielectric constant (DC) and loss tangent (sometimes also called dissipation factor (DF)) were measured according to ASTM D-2520 Method B – Resonant Cavity Perturbation Technique. The nominal sample size of the test specimen was 1.78 × 2.54 × 25.4 mm. The tests were conducted under laboratory environmental conditions (23°C and 51% RH nominal value).

[0193] Preferably, the thermoplastic resin has a melt flow rate of MFR1 measured at 300°C and 1.2 kg according to ISO 1133-1:2011, and the composition according to the invention has a melt flow rate of MFR2 measured at 300°C and 1.2 kg according to ISO 1133-1:2011, wherein MFR2 is at most 130% of MFR1.

[0194] High flame retardancy implementation plan

[0195] Lower amounts of b) and c) were found to result in better flame retardancy. In this case, the desired flame retardancy can be achieved even in the (virtually) absence of flame retardant e).

[0196] Therefore, in some embodiments, the amount of b1), b2), or the sum of b1) and b2) relative to the total composition is at least 0.1% by weight and at most 20% by weight, preferably at least 1.0% by weight, at least 3.0% by weight or at least 5.0% by weight, and / or at most 19% by weight, at most 18% by weight, at most 17% by weight, at most 16% by weight, at most 16% by weight or at most 15% by weight.

[0197] In some embodiments, the amount of b) relative to the total composition is at least 0.1% by weight and at most 20% by weight, preferably at least 1.0% by weight, at least 3.0% by weight or at least 5.0% by weight, and / or at most 19% by weight, at most 18% by weight, at most 17% by weight, at most 16% by weight, at most 16% by weight or at most 15% by weight.

[0198] In some embodiments, the amount of c) relative to the total composition is at most 30% by weight, at most 25% by weight, at most 20% by weight, at most 15% by weight, at most 10% by weight, less than 10% by weight, at most 9% by weight, at most 8% by weight, at most 5% by weight, at most 3% by weight, at most 1% by weight, or 0% by weight.

[0199] In some embodiments, the total amounts of b1), b2), and c) relative to the total composition are less than 35% by weight, up to 30% by weight, up to 25% by weight, up to 20% by weight, up to 15% by weight, up to 10% by weight, less than 10% by weight, up to 9% by weight, up to 8% by weight, up to 5% by weight, up to 3% by weight, up to 1% by weight, or 0% by weight relative to the total composition.

[0200] In some embodiments, the total amounts of b) and c) relative to the total composition are less than 35% by weight, up to 30% by weight, up to 25% by weight, up to 20% by weight, up to 15% by weight, up to 10% by weight, less than 10% by weight, up to 9% by weight, up to 8% by weight, up to 5% by weight, up to 3% by weight, up to 1% by weight, or 0% by weight relative to the total composition.

[0201] In these embodiments, preferably, the molded part of the composition has a UL94 V2, V1, or V0 rating at a thickness of 1.5 mm (±10%) and / or a UL94 V2, V1, or V0 rating at a thickness of 3.0 mm (±10%). The composition may or may not contain a flame retardant. When the composition contains a flame retardant, the amount of the flame retardant relative to the total composition may be, for example, at least 0.01 wt% and / or at most 5 wt%, at most 1.0 wt%, at most 0.5 wt%, at most 0.1 wt%, at most 0.05 wt%, or at most 0.01 wt%.

[0202] Other aspects

[0203] The present invention also relates to molded parts comprising a thermoplastic composition according to the invention. The invention particularly relates to molded parts produced by injection molding a composition according to the invention. The invention also relates to articles, particularly circuit carriers, comprising molded parts produced by a composition according to the invention and conductive rails provided thereon. In one embodiment, such a circuit carrier is used in the production of an antenna.

[0204] The present invention also relates to a method for manufacturing such a circuit carrier, the method comprising the steps of: providing a molded part comprising a thermoplastic composition according to the invention, irradiating the part with laser radiation to an area thereon on which conductive rails are to be formed, and subsequently metallizing the irradiated area. In a preferred embodiment, laser irradiation is used to simultaneously release a metal nucleus and ablate the part, while simultaneously forming a surface that promotes adhesion. This provides a simple means of achieving excellent adhesive strength of the deposited metal conductor rails. Advantageously, the wavelength of the laser is 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm, or even 10600 nm. Deposition of other metals on the metal nucleus generated by laser irradiation is preferably performed by a plating process. The metallization is preferably performed by immersing the molded part in at least one chemical plating bath to form conductive pathways on the irradiated area of ​​the molded part. Non-limiting examples of chemical plating processes are copper plating, gold plating, nickel plating, silver plating, zinc plating, and tin plating. Preferably, the first plating is copper plating. The conductive rails may have one or more layers. The first layer may be, for example, a copper layer, and may be 8-16 μm, more typically 8-12 μm. If present, the second layer may be, for example, a nickel layer, and may be 2-4 μm. If present, the third layer may be, for example, a gold layer, and may be 0.05-0.2 μm.

[0205] Irradiation of molded parts can be carried out, for example, under conditions including a power of 2-15W, a frequency of 20-100kHz, and / or a speed of 1-5m / s.

[0206] Irradiation of molded parts can be performed, for example, by UV light with a wavelength of 100 to 400 nm, visible light with a wavelength of 400 to 800 nm, or infrared light with a wavelength of 800 to 25,000 nm.

[0207] When irradiating molded parts with UV light of wavelengths of 100-400 nm, it is preferable to subject the molded parts with metallized regions to heat treatment to improve delamination resistance. Heat treatment can be performed by subjecting the molded parts to microwaves (e.g., by placing the molded parts in a microwave oven). Preferably, the irradiation of the molded parts is performed with visible light of wavelengths of 400 to 800 nm or infrared light of wavelengths of 800 to 25,000 nm. These types of laser radiation are advantageous because the metal layer on the irradiated area has relatively strong adhesion strength, eliminating the need for heat treatment after the plating step. Most preferably, the irradiation of the molded parts is performed with infrared light of wavelengths of 800 to 25,000 nm, particularly 1064 nm.

[0208] Preferably, the method for manufacturing the circuit carrier does not include a heat treatment step after the step of metallizing the irradiated area. This is advantageous considering the permissible method.

[0209] Another aspect of the invention relates to a thermoplastic composition according to the invention for use in a laser direct structuring method.

[0210] Another aspect of the invention relates to the use of the thermoplastic composition according to the invention in a laser direct structuring method.

[0211] Note that the present invention relates to the subject matter defined in the independent claims, which may be combined individually or in any possible combination of features described herein, particularly those combinations of features present in the claims. Therefore, it will be understood that all combinations of features related to the composition according to the invention; all combinations of features related to the method according to the invention; and all combinations of features related to the composition according to the invention and features related to the method according to the invention are described herein. Therefore, it will be understood that combinations of features related to the molding step, irradiation step, and metallization step of the method according to the invention and features related to the composition according to the invention are described herein. For example, this specification discloses a method for manufacturing a circuit carrier, comprising providing a molded part comprising a thermoplastic composition according to the invention; irradiating the part with laser radiation to form a region thereon on which conductive rails are to be formed; and subsequently metallizing the irradiated region, wherein the composition comprises component d), and the irradiation of the molded part is performed by infrared light having a wavelength of 800 to 25,000 nm.

[0212] It should also be noted that the term "comprising" does not exclude the presence of other elements. However, it should be understood that a description of a product comprising certain components also discloses a product composed of those components. Similarly, it should be understood that a description of a method comprising certain steps also discloses a method composed of those steps. A product / composition composed of these components may be advantageous because it provides a simpler and more economical method for preparing said product / composition. Similarly, it should be understood that a description of a method comprising certain steps also discloses a method composed of those steps. A method composed of those steps may be advantageous because it provides a simpler and more economical method.

[0213] When the lower and upper limits of a parameter are mentioned, the range formed by the combination of the lower and upper limits is also understood to be disclosed.

[0214] The present invention is illustrated by the following embodiments, but is not limited thereto.

[0215] experiment

[0216] The comparative experiments (CEx) and example compositions (Ex) were prepared from the components given in Table 1.

[0217] All sample compositions were prepared according to the amounts given in Tables 2 to 4. All amounts are weight percentages. In each experiment, the sample was extruded on a co-rotating twin-screw extruder at a temperature of 280°C. The extrudate was granulated, and the collected granules were dried at 110°C for 4 hours and then injection molded into test parts at a melt temperature of approximately 290°C–300°C.

[0218] Radio frequency properties – dielectric constant (DC) and dissipation factor (DF) – measured at 6 GHz using ASTM D-2520 Method B – Guidelines for resonant cavity perturbation techniques. The nominal sample size of the test specimen was 1.78 x 2.54 x 25.4 mm. Testing was conducted under laboratory environmental conditions (23°C and 51% RH nominal value).

[0219] After storing the samples at 23°C and 50% relative humidity for 48 hours, their flammability was determined according to the UL 94V method. For each sample, five test specimens were tested. In addition to the UL 94V rating (V-0, V-1, V-2, or NC (=no rating)), the total afterflame time (FOT) was recorded, which is the sum of the afterflame time of the first (t1) and second (t2) flame contacts of the five tested specimens.

[0220] The degree of resin degradation after compounding is confirmed by measuring the melt flow rate (MFR) of the resin before compounding and the composition prepared by compounding the resin at 300°C / 1.2 kg, according to ISO 1133. The presence of ceramic fillers in the composition generally results in a lower MFR. Therefore, if no polymer degradation occurs during compounding, the MFR of the composition will typically be lower than the MFR of the resin. Thus, the increased MFR after compounding is attributed to resin degradation.

[0221] The degree of resin degradation after compounding was further determined by measuring the Vicat temperature and Izod notched impact strength of the resin before compounding and the composition prepared by compounding the resin. The decreased Vicat temperature and decreased impact strength were both attributed to resin degradation.

[0222] Table 1

[0223]

[0224] Table 2

[0225]

[0226]

[0227] Table 2 shows the results using the most commonly used LDS additives, copper chromium oxide spinel, and antimony-doped tin oxide.

[0228] In Comparative Examples 1 and 2, which used small amounts of LDS additive, the composition's MFR was lower than that of the resin, indicating that the resin did not undergo excessive degradation. The same conclusion can be drawn from the MV viscosity under high shear, Vicat temperature, and cantilever beam notched impact strength.

[0229] In Comparative Examples 1 and 2, the desired dielectric properties were obtained, particularly a dielectric constant of at least 4.0 at 6 GHz.

[0230] However, the desired flame retardancy was not achieved in Comparative Example 1 and Comparative Example 2.

[0231] In Comparative Example 3, which used a large amount of CuCr, it is understood that no excessive degradation of the resin occurred. However, the dielectric constant was not very high, below 1.0 at 6 GHz. The desired flame retardancy was achieved.

[0232] In Comparative Example 4, where a large amount of ATO was used, it is understood that excessive degradation of the resin had occurred. The MFR of the composition was greater than 200% of the MFR of the resin. Furthermore, although the desired dielectric properties were obtained, the desired flame retardancy was not achieved.

[0233] Therefore, it can be concluded that the use of copper chromite or ATO did not result in the desired combination of properties.

[0234] Table 3

[0235]

[0236]

[0237] Table 3 shows the results using aluminum-doped zinc oxide (AZO) according to the present invention.

[0238] In Comparative Example 5, which used AZO but not wax, the desired dielectric properties and flame retardancy were obtained. However, it is understood that excessive degradation of the resin has occurred. The MFR of the composition was too high to be measured. The degradation was also confirmed by MV, Vicat temperature, and cantilever beam notched impact strength.

[0239] In contrast, in Example 1, where AZO was used in conjunction with wax, no excessive degradation of the resin occurred. The desired dielectric properties and desired flame retardancy were also achieved.

[0240] It is remarkable that Comparative Example 6 used ATO with wax instead of AZO as in Example 1. Comparative Example 6 showed that the wax did not prevent excessive degradation of the resin caused by ATO. Nor did it achieve the desired flame retardancy. Therefore, it can be concluded that specific LDS additives combined with wax result in a combination of desired properties.

[0241] Examples 2 and 3 also exhibit a combination of desired properties. It is understood that a higher DC can be obtained by using a large amount of TiO2, and it is also understood that the DC is still high even without using a large amount of TiO2. A comparison between Examples 2 and 3 shows that the type of ceramic filler (TiO2 or BST) did not lead to significant differences.

[0242] Table 4

[0243]

[0244]

[0245] A comparison between Examples 4 and 5 shows that a smaller amount of wax is beneficial for flame retardancy.

[0246] A comparison between Example 4 and Example 6 shows that a smaller amount of TiO2 is beneficial to flame retardancy.

[0247] A comparison between Examples 4 and 7 shows that a larger amount of PC relative to AZO is beneficial to impact strength.

[0248] A comparison between Example 4 and Example 6 shows that a larger amount of TiO2 is beneficial to DC.

[0249] A comparison between Example 5 and Example 7 shows that a larger amount of ATO is beneficial to DC.

[0250] Table 5

[0251]

[0252]

[0253] A comparison between Example 4 and Example 8 shows that the addition of ATO reduces flame retardancy.

[0254] A comparison between Example 4 and Example 9 shows that the addition of a small amount of CuCr2O4 does not substantially change the properties.

[0255] Table 6

[0256]

[0257]

[0258] Table 6 shows the results using calcium copper titanate (CCTO) according to the present invention.

[0259] Similar to the experiment using AZO, Comparative Example 7, which did not contain wax, showed a very high MFI and a very low cantilever beam impact strength due to polymer degradation.

[0260] Example 10, with the addition of a small amount of wax, surprisingly showed no degradation (low MFI / high MV, high impact strength) while exhibiting excellent flame retardancy. Furthermore, high DC was achieved through Example 10.

[0261] Example 11, which uses different types of flame retardants, demonstrates a combination of desired properties. The flame retardancy is even better than in Example 10.

[0262] Comparative Example 8 shows that the addition of MZP has some effect in preventing polymer degradation, but its effect is very limited compared to the use of the wax according to the invention.

Claims

1. A thermoplastic composition comprising: a) 20 to 90 wt.-% of a thermoplastic resin, wherein the thermoplastic resin is polycarbonate or a blend of polycarbonate and a rubbery polymer, wherein the rubbery polymer contains an elastomeric polymer having a Tg of less than 10 °C, b) a laser direct structuring additive, c) optionally, ceramic filler particles not having a laser direct structuring additive function, and d) 0.1 to 5.0 wt.-% of a maleic anhydride modified polyethylene, wherein b) comprises b1 ) an electrically conductive metal oxide, wherein the electrically conductive metal oxide has a resistivity of at most 5 x 10 3 Ω - cm and contains at least a metal of group n and a metal of group n+1 of the periodic table, wherein n is an integer from 3 to 13, and / or b2) calcium copper titanate.

2. The composition according to claim 1, wherein the rubbery polymer is an elastomeric polymer having a Tg of less than 10 °C.

3. The composition according to claim 1, wherein the elastomeric polymer has a Tg of less than -10 °C.

4. The composition according to claim 1, wherein the elastomeric polymer has a Tg of -20 °C to -80 °C.

5. The composition according to claim 1, wherein the amount of rubbery polymer in the thermoplastic resin a) is 0 to 60 wt.-% of the amount of the thermoplastic resin a).

6. The composition according to claim 1, wherein the amount of rubbery polymer in the thermoplastic resin a) is 1 to 50 wt.-% of the amount of the thermoplastic resin a).

7. The composition according to claim 1, wherein the amount of rubbery polymer in the thermoplastic resin a) is 5 to 40 wt.-% of the amount of the thermoplastic resin a).

8. The composition according to claim 1, wherein the amount of rubbery polymer in the thermoplastic resin a) is 10 to 30 wt.-% of the amount of the thermoplastic resin a).

9. The composition according to any one of claims 1 to 8, wherein the elastomeric polymer comprises an ABS resin, i.e. acrylonitrile-butadiene-styrene copolymer, an AES resin, i.e. acrylonitrile-ethylene-propylene-styrene copolymer, an AAS resin, i.e. acrylonitrile-acrylic elastomer-styrene copolymer, and MBS, i.e. methyl methacrylate butadiene styrene copolymer.

10. The composition according to claim 1, wherein a) is a blend of - 45 to 75 wt.-% of polycarbonate, 5 to 40 wt.-% of ABS, and 0 to 10 wt.-% of MBS, wherein the amounts are relative to the thermoplastic resin a), or - 80 to 99 wt.-% of polycarbonate and 1 to 20 wt.-% of a graft copolymer comprising an Si containing elastomeric component, wherein the amounts are relative to the thermoplastic resin a).

11. The composition according to claim 10, wherein a) is - a blend consisting of 45 to 75 wt.-% of polycarbonate and 5 to 40 wt.-% of ABS, wherein the amounts are relative to the thermoplastic resin a), or - a blend consisting of 45 to 75 wt.-% of polycarbonate, 5 to 40 wt.-% of ABS, and 1 to 10 wt.-% of MBS, wherein the amounts are relative to the thermoplastic resin a), or - a blend consisting of 80 to 99 wt.-% of polycarbonate and 1 to 20 wt.-% of a graft copolymer comprising an Si containing elastomeric component, wherein the amounts are relative to the thermoplastic resin a). ​ ​ - a blend consisting of 80 to 99 wt.-% of polycarbonate and 1 to 20 wt.-% of a graft copolymer comprising a Si-containing elastomer component, wherein the graft copolymer is a core / shell graft copolymer, wherein the core is a polyorganosiloxane, wherein the amounts are relative to the thermoplastic resin a).

12. The composition according to any one of claims 1 to 8, wherein b1 ) the electrically conductive metal oxide has an electrical resistivity of 8 x 10 2 Ω - cm or less.

13. The composition according to claim 12, wherein b1 ) the electrically conductive metal oxide has a specific resistance of 7 x 10 2 Ω - cm or less.

14. The composition according to claim 12, wherein b1 ) the electrically conductive metal oxide has a specific resistance of 5 x 10 2 Ω - cm or less.

15. The composition according to any one of claims 1 to 8, wherein n is an integer from 10 to 13.

16. The composition according to claim 15, wherein n is 12 or 13.

17. The composition according to claim 15, wherein n is 12.

18. The composition according to claim 15, wherein the metal of group n is zinc and the metal of group n+1 is aluminum.

19. The composition according to claim 15, wherein the electrically conductive metal oxide is aluminum-doped zinc oxide.

20. The composition according to claim 15, wherein the amount of the metal of group n is 15 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide, or the amount of the metal of group n+1 is 15 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide.

21. The composition according to claim 20, wherein the amount of the metal of group n is 12 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide.

22. The composition according to claim 20, wherein the amount of the metal of group n is 10 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide.

23. The composition according to claim 20, wherein the amount of the metal of group n+1 is 12 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide.

24. The composition according to claim 20, wherein the amount of the metal of group n+1 is 10 mole% or less relative to the total amount of the metal of group n and the metal of group n+1 in the electrically conductive metal oxide.

25. The composition according to any one of claims 1 to 8, wherein b) comprises particles of b1) and / or particles of b2).

26. The composition according to claim 25, wherein the amount of the particles of b1), the amount of the particles of b2), or the total amount of the particles of b1) and b2) is from 10 to 100 wt.-% relative to the amount of b).

27. The composition according to claim 25, wherein the amount of the particles of b1), the amount of the particles of b2), or the total amount of the particles of b1) and b2) is at least 50 wt.-% relative to the amount of b).

28. The composition according to claim 25, wherein the amount of the particles of b1), the amount of the particles of b2), or the total amount of the particles of b1) and b2) is at least 60 wt.-% relative to the amount of b).

29. The composition according to claim 25, wherein the amount of the particles of b1), the amount of the particles of b2), or the total amount of the particles of b1) and b2) is at least 70 wt.-% relative to the amount of b).

30. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 80 wt.%, relative to the amount of b).

31. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 90 wt.%, relative to the amount of b).

32. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 95 wt.%, relative to the amount of b).

33. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 98 wt.%, relative to the amount of b).

34. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 99.0 wt.%, relative to the amount of b).

35. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 99.5 wt.%, relative to the amount of b).

36. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is at least 99.9 wt.%, relative to the amount of b).

37. The composition of claim 25, wherein the amount of particles of b1), the amount of particles of b2), or the total amount of particles of b1) and b2) is 100 wt.%, relative to the amount of b).

38. The composition of any one of claims 1-8, wherein the amount of b1), b2), or the sum of b1) and b2) is 0.1 to 80 wt.%, relative to the total composition.

39. The composition of claim 38, wherein the amount of b1), b2), or the sum of b1) and b2) is at least 31 wt.%, relative to the total composition.

40. The composition of any one of claims 1-8, wherein the amount of d) is 0.3 to 3.0 wt.%, relative to the total composition.

41. The composition of claim 40, wherein the amount of d) is 0.5 to 1.5 wt.%, relative to the total composition.

42. The composition of any one of claims 1-8, wherein the molded parts of the composition have a UL94 V2, VI, or VO rating at a thickness of 1.5 mm (±10%).

43. The composition of claim 42, wherein the composition comprises e) a flame retardant, wherein the amount of the flame retardant is 0.01 to 5.0 wt.%, relative to the total composition.

44. The composition of any one of claims 1-8, wherein the amount of c) is less than 10 wt.%, relative to the total composition.

45. The composition of claim 44, wherein the amount of c) is at least 0.1 wt% relative to the total composition.

46. The composition of claim 45, wherein the amount of c) is at least 1.0 wt% relative to the total composition.

47. The composition of claim 45, wherein the amount of c) is at least 3.0 wt% relative to the total composition.

48. The composition of any one of claims 1-8, wherein the ceramic filler particles are selected from the group consisting of metal oxides, metal silicates, metal borides, metal carbides, and metal nitrides.

49. The composition of claim 48, wherein the ceramic filler particles are metal oxides.

50. The composition of claim 49, wherein the ceramic filler particles are one or more selected from the group consisting of titanium dioxide, barium titanate, barium strontium titanate.

51. The composition of any one of claims 1-8, wherein the composition has a dielectric constant of at least 4.0 measured at 1 GHz, and / or wherein the composition has a loss tangent of at most 0.014 measured at 1 GHz, and / or wherein the composition has a dielectric constant of at least 4.2 measured at 6 GHz, and / or wherein the composition has a loss tangent of at most 0.014 measured at 6 GHz, and / or wherein the composition has a dielectric constant of at least 3.5 measured at 40 GHz, and / or wherein the composition has a loss tangent of at most 0.014 measured at 40 GHz, wherein the dielectric constant and the loss tangent are measured according to ASTM D-2520 Method B.

52. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.2 measured at 1 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

53. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.5 measured at 1 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

54. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.7 measured at 1 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

55. The composition of claim 51, wherein the composition has a dielectric constant of at least 5.0 measured at 1 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

56. The composition of claim 51, wherein the composition has a loss tangent of at most 0.010 measured at 1 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

57. The composition of claim 51, wherein the composition has a loss tangent of at most 0.007 measured at 1 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

58. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.5 measured at 6 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

59. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.7 measured at 6 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

60. The composition of claim 51, wherein the composition has a dielectric constant of at least 5.0 measured at 6 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

61. The composition of claim 51, wherein the composition has a loss tangent of at most 0.010 measured at 6 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

62. The composition of claim 51, wherein the composition has a loss tangent of at most 0.007 measured at 6 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

63. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.0 measured at 40 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

64. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.2 measured at 40 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

65. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.5 measured at 40 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

66. The composition of claim 51, wherein the composition has a dielectric constant of at least 4.7 measured at 40 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

67. The composition of claim 51, wherein the composition has a dielectric constant of at least 5.0 measured at 40 GHz, wherein the dielectric constant is measured according to ASTM D-2520 Method B.

68. The composition of claim 51, wherein the composition has a loss tangent of at most 0.010 measured at 40 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

69. The composition of claim 51, wherein the composition has a loss tangent of at most 0.007 measured at 40 GHz, wherein the loss tangent is measured according to ASTM D-2520 Method B.

70. The composition according to any one of claims 1 to 8, wherein the total amount of b1) and b2) and c) is at least 35 wt.-%, relative to the total composition.

71. The composition according to claim 70, wherein the total amount of b1) and b2) and c) is at least 40 wt.-%, relative to the total composition.

72. The composition according to claim 70, wherein the total amount of b1), b2) and c) is at most 70 wt.-%, relative to the total composition.

73. The composition according to claim 72, wherein the total amount of b1), b2) and c) is at most 65 wt.-%, relative to the total composition.

74. The composition according to any one of claims 1 to 8, wherein the composition comprises less than 2.5 wt.-%, relative to the total composition, of a rubbery polymer.

75. The composition according to any one of claims 1 to 8, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.

0.

76. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.

2.

77. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.

5.

78. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.

8.

79. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 2.

0.

80. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 2.

5.

81. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 3.

0.

82. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 3.

5.

83. The composition according to claim 75, wherein the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 4.

0.

84. The composition according to any one of claims 1 to 8, wherein the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.

0.

85. The composition according to claim 84, wherein the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.

2.

86. The composition according to claim 84, wherein the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.

5.

87. The composition according to claim 84, wherein the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.

8.

88. The composition according to claim 84, wherein the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 2.

0.

89. The composition according to claim 84, wherein the weight ratio of the total amount of b1 ) and b2) to the amount of c) in the composition is at least 2.

5.

90. The composition according to claim 84, wherein the weight ratio of the total amount of b1 ) and b2) to the amount of c) in the composition is at least 3.

0.

91. The composition according to claim 84, wherein the weight ratio of the total amount of b1 ) and b2) to the amount of c) in the composition is at least 3.

5.

92. The composition according to claim 84, wherein the weight ratio of the total amount of b1 ) and b2) to the amount of c) in the composition is at least 4.

0.

93. The composition according to any one of claims 1 to 8, wherein the total amount of components a), b) and c) is 90 to 99.9 wt.-% of the total composition.

94. The composition according to claim 93, wherein the total amount of components a), b) and c) is 95 to 99 wt.-% of the total composition.

95. The composition according to any one of claims 1 to 8, wherein the total amount of components a), b), c) and d) is 90 to 100 wt.-% of the total composition.

96. The composition according to claim 95, wherein the total amount of components a), b), c) and d) is 90 to 99.9 wt.-% of the total composition.

97. The composition according to claim 95, wherein the total amount of components a), b), c) and d) is 92 to 99.0 wt.-% of the total composition.

98. The composition according to claim 95, wherein the total amount of components a), b), c) and d) is 95 to 98 wt.-% of the total composition.

99. A molded part comprising the composition according to any one of claims 1 to 98.

100. A process for manufacturing a circuit carrier, comprising providing a molded part according to claim 99; irradiating the area of the part on which the electrically conductive tracks are to be formed with laser radiation; and subsequently metallizing the irradiated area.

101. A circuit carrier obtainable by the process according to claim 100.

102. An antenna comprising the circuit carrier according to claim 101.

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